Chemistry Letters 2002
171
Table 1. Reactions of 3 (Y¼CN) with various aldehydes
Entry
R
Conditionsa
Z : E
Yield/%
Dedicated to Prof. Teruaki Mukaiyama on the occasion of his
1
2
C6H5
A
B
A
B
A
B
A
B
A
A
B
2
66 : 34
77 : 23
69 : 31
82 : 18
67 : 33
72 : 28
90 : 10
98 : 2
96
47b
81
46b
85
37b
85
93
93
94
84
85
75th birthday.
3
4-(NO2)C6H4
4-ClC6H4
References and Notes
4
5
#
Present address: Advanced Research Center for Science and Engineer-
ing, Waseda University, 3-4-1Ohkubo, Shinjuku-ku, Tokyo 169-8555,
Japan. Tel & Fax þ81-3-5286-3165. E-mail: akibaky@mn.waseda.ac.jp
6
1For leading references see: a) W. S. Wadsworth Jr.,
Org. React., 25, 73
7
8
2-ClC6H4
(1977). b) J. I. G. Cadogan, ‘‘Organophosphorus Reagents in Organic
Synthesis,’’ Academic Press, New York (1979). c) B. E. Maryanoff and
A. B. Reitz, Chem. Rev., 89, 863 (1989). d) S. E. Kelly, ‘‘Comprehensive
Organic Synthesis,’’ ed. by B. M. Trost, I. Fleming, Pergamon Press, Oxford
(1991) Vol. 1, p 730. e) A. W. Johnson, ‘‘Ylides and Imines of
Phosphorus,’’ Wiley-Interscience, New York (1993). f) O. I. Kolodiazhnyi,
‘‘Phosphorus Ylides,’’ Wiley-VCH, Weinheim (1999). g) K. Ando, J. Synth.
Org. Chem., Jpn., 58, 869 (2000).
9
2,6-Cl2C6H3
PhCH2CH2
18 : 82
76 : 24
87 : 13
91 : 9
10
11
1
C
1
3
94 : 6
93 : 7
87
98
D
14
1
16
1
PhMeCH
A
5
E
2
3
M. L. Bojin, S. Barkallah, and S. A. Evans, Jr., J. Am. Chem. Soc., 118, 1549
(1996).
a) S. Kojima and K.-y. Akiba, Tetrahedron Lett., 38, 547 (1997). b) S.
Kojima, R. Takagi, and K.-y. Akiba, J. Am. Chem. Soc., 119, 5970 (1997). c)
S. Kojima, K. Kawaguchi, and K.-y. Akiba, Tetrahedron Lett., 38, 7753
(1997).
99 : 1
95 : 5
43 : 57
100
97
B
PhMe2C
7 E)-PhC(H¼CH
A
97
aCondition A: 0 ꢁC, 1h. Condition B: À78 ꢁC, 30 min, then rt, 30 min
(the cooling bath was removed). Condition C: À78 ꢁC, 36 h, then rt,
30 min (the cooling bath was removed). Condition D: À78 ꢁC, then rt, 9 h
(without removal of the cooling bath). Condition E: 0 ꢁC, then rt,
overnight (without removal of the cooling bath). bThe yield was not
optimized.
4
5
T. Kawashima, K. Watanabe, and R. Okazaki, Tetrahedron Lett., 38, 551
(1997).
´
´
F. Carre, M. Chauhan, C. Chuit, R. J. P. Corriu, and C. Reye, Phosphorus
Sulfur Silicon, 123, 181 (1997).
6
7
Z. Wang and J. G. Verkade, Tetrahedron Lett., 39, 9331(1998).
‘‘Chemistry of Hypervalent Compounds,’’ ed. by K.-y. Akiba, Wiley-VCH,
New York (1999).
8
9
J. C. Martin, Science, 221, 509 (1983) and references therein.
a) Y. Yamakado, M. Ishiguro, N. Ikeda, and H. Yamamoto, J. Am. Chem.
Soc., 103, 5568 (1981). b) R. Haruta, M. Ishiguro, K. Furuta, A. Mori, N.
Ikeda, and H. Yamamoto, Chem. Lett., 1982, 1093. c) K. Furuta, M. Ishiguro,
R. Haruta, A. Mori, N. Ikeda, and H. Yamamoto, Bull. Chem. Soc. Jpn., 57,
2768 (1984).
formyl group, the selectivity was uniformly high. The reaction of
the unsaturated cinnamaldehyde was unfortunately unselective.
Table 2. Reactions of amides 4 and 5 with various aldehydesa
Entry
1CONMe
2
3
4
5
6
Y
R
Z : E
Yield/%
10 T. Y. Zhang, J. C. O’Toole, and J. M. Dunigan, Tetrahedron Lett., 39, 1461
(1998).
C6H5
<99 : <1
99 : 1
99 : 1
84
67
66
71
70
92
2
PhCH2CH2
PhMeCH
C6H5
11 W. C. Still and C. Gennari, Tetrahedron Lett., 24, 4405 (1983).
12 a) K. Ando, Tetrahedron Lett., 36, 4105 (1995). b) K. Ando, J. Org. Chem.,
62, 1934 (1997). c) K. Ando, J. Org. Chem., 63, 8411 (1998). d) K. Ando, J.
Org. Chem., 64, 8406 (1999). e) K. Ando, J. Org. Chem., 65, 4745 (2000).
13 K. Kokin, J. Motoyoshiya, S. Hayashi, and H. Aoyama, Synth. Commun., 27,
2387 (1997).
14 W. Yu, M. Su, and Z. Jin, Tetrahedron Lett., 40, 6725 (1999).
15 S. Kojima, H. Inai, T. Hidaka, and K. Ohkata, Chem. Commun., 2000, 1795.
16 K. Ando, Synlett, 2001, 1272.
CONH2
99 : 1
99 : 1
>99 : <1
PhCH2CH2
PhMeCH
aAll reactions were carried out at rt.
Next examined were amide based reagents 4 (Y ¼ CONMe2)
and 5 (Y ¼ CONH2). Of high expectations was the latter reagent,
since the presence of hydrogen atoms would in principle allow
further functionalization and no attempts on unsubstituted amides
had previously been reported. Since amides are generally more
bulky than esters, predictions were that the reaction would become
sluggish and that the selectivity would diminish somewhat as seen
with HWE type reagents.16;17 Fortunately for us, however, the
reaction carried out at rt with aldehydes furnished the corresponding
disubstituted ꢀ; ꢁ-unsaturated amides without event and the Z-
selectivity was exceptionally high for both aromatic and aliphatic
aldehydes, as tabulated in Table 2. For 5, although both the reagent
and olefinic products bear active hydrogens on nitrogen, excess
amounts of base were not required.
In summary, we have found that spirophosphoranes 3-5
undergo Wittig type reactions with aldehydes to give the
corresponding ꢀ; ꢁ-unsaturated cyanides and amides with practical
levels of Z-selectivity in the case of 3 with aliphatic aldehydes
(Z : E ¼ 94 : 6 to 99 : 1), and 4 or 5 with both aromatic and
aliphatic aldehydes (Z : E ¼ 99 : 1 to >99 : <1).
17 S. Kojima, T. Hidaka, Y. Ohba, and K. Ohkata, Phosphorus Sulfur Silicon,
179, 191 (2001).
18 a) I. Granoth and J. C. Martin, J. Am. Chem. Soc., 101, 4418 and 4623 (1979).
b) E. F. Perozzi, R. S. Michalak, G. D. Figuly, W. H. Stevenson, III, D. B.
Dess, M. R. Ross, and J. C. Martin, J. Org. Chem., 46, 1049 (1981).
19 a) S. Kojima, K. Kajiyama, and K.-y. Akiba, Tetrahedron Lett., 35, 7037
(1994). b) S. Kojima, K. Kajiyama, and K.-y. Akiba, Bull. Chem. Soc. Jpn.,
68, 1785 (1995).
20 3: Mp 114–117 ꢁC. 1H NMR (400 MHz, CDCl3, ꢂ) 8.44 (dd, J ¼ 11:6,
7.3 Hz, 2H), 7.84–7.75 (m, 6H), 3.47 (dd, 2JPH ¼ 22:7 Hz, 2JHH ¼ 16:4 Hz,
1H), 3.22 (dd, 2JPH ¼ 15:2 Hz, 2JHH ¼ 16:4 Hz, 1H); 19F NMR (376 MHz,
CDCl3, ꢂ) À75:0 (q, 4JFF ¼ 8:5 Hz, 6F), À75:1 (q, 4JFF ¼ 8:5 Hz, 6F); 31
P
NMR (162 MHz, CDCl3, ꢂ) À30:6; Anal. Calcd for C20H10F12NO2P: C,
43.26, H, 1.82; N, 2.52%. Found: C, 42.96; H, 1.75; N, 2.30%. 4: Mp 158–
159 ꢁC. 1H NMR (400 MHz, CDCl3, ꢂ) 8.48–8.44 (m, 2H), 7.72–7.68 (m,
2
2
2
6H), 3.68 (dd, JPH ¼ 18:5 Hz, JHH ¼ 15:1 Hz, 1H), 3.52 (dd, JPH
¼
18:0 Hz, JHH ¼ 15:1 Hz, 1H), 2.91 (s, 3H), 2.85 (s, 3H); 19F NMR
(376 MHz, CDCl3, ꢂ) À74:5 (q, JFF ¼ 9:5 Hz, 6F), À75:2 (q, JFF
9:5 Hz, 6F); 31P NMR (162 MHz, CDCl3, ꢂ) À24:5; Anal. Calcd for
2
4
4
¼
C
22H16F12NO3P: C, 43.94, H, 2.68; N, 2.33%. Found: C, 43.58; H, 2.49; N,
2.24%. 5: Mp 198–199 ꢁC. 1H NMR (400 MHz, CDCl3, ꢂ) 8.43–8.38 (m,
2
2H), 7.76–7.70 (m, 6H), 6.02 (bs, 1H), 5.31 (bs, 1H), 3.45 (dd, JPH
¼
21:0 Hz, 2JHH ¼ 13:7 Hz, 1H), 3.29 (dd, JPH ¼ 14:2 Hz, 2JHH ¼ 13:7 Hz,
1H); 19F NMR (376 MHz, CDCl3, ꢂ) À74:8 (q, 4JFF ¼ 9:2 Hz, 6F), À75:0 (q,
4JFF ¼ 9:2 Hz, 6F); 31P NMR (162 MHz, CDCl3, ꢂ) À27:1; Anal. Calcd for
2
C
20H12F12NO3P: C, 41.90, H, 2.11; N, 2.44%. Found: C, 41.92; H, 2.04; N,
2.36%.
The authors are grateful to Central Glass Co. Ltd. for supplying
us with hexafluorocumyl alcohol.